CN105713262B - A kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe - Google Patents

A kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe Download PDF

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CN105713262B
CN105713262B CN201610229505.4A CN201610229505A CN105713262B CN 105713262 B CN105713262 B CN 105713262B CN 201610229505 A CN201610229505 A CN 201610229505A CN 105713262 B CN105713262 B CN 105713262B
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weight
parts
foaming
sole
styrene rubber
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CN105713262A (en
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邵亮
姬占有
马建中
薛朝华
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The present invention relates to the preparation method of Foamed Sole Materials, and in particular to a kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe.Using compounding cross-linking system（Sulphur cumyl peroxide）SBR foaming sole materials are prepared, the foaming sole material has excellent anti-contracility, the characteristics of embodying low-density and compress askew small, and with relatively low cost, disclosure satisfy that other same performances use the requirement in field.Banburying is blended in SBR and white carbon and zinc oxide by the present invention；The addition banburying such as foaming agent, crosslinking agent, accelerator and paraffin is obtained into mill at mixture, 70 DEG C again and is pressed into sheet material；The aqueous emulsion release agents of polysiloxanes are sprayed, molding crosslinked foaming shaping slice is carried out.SBR expanded materials prepared by the present invention have excellent performance, and its shrinkage factor can be reduced to 2%, density for 0.21 0.35 g/cm3, compress it is askew be 15 25%, hardness（A）It is 55 60% for 50 60 °, resilience.

Description

A kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe
First, technical field：
The present invention relates to the preparation method of Foamed Sole Materials, and in particular to a kind of low-shrinkage butadiene styrene rubber foaming sole The preparation technology of material.
2nd, background technology：
SBR rubber expanded material product has the advantages that traditional rubber is incomparable as the material of novel environment friendly, its The very big market advantage is shown in kind, quality and price.Because the presence of gas phase has, density is low, specific strength is high, energy for it The advantages of absorbing load, and with excellent pliability, warming, waterproof, shockproof and good wearability, ageing-resistant, therefore It is widely used in the fields such as footwear material, diving suit, motion medical equipment, insulation material.
Foaming sole material special requirement shrinkage factor is small, compression set is small（Compression is askew）, density it is low and ageing-resistant, Hardness is moderate, but general butadiene styrene rubber foaming material for sole of shoe shrinkage factor is big（10% or so）, yield rate is low.
3rd, the content of the invention
A kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe of offer of the present invention, using compounding crosslinked System（Sulphur-cumyl peroxide）SBR foaming sole materials are prepared, the foaming sole material has excellent anti-contracility, The characteristics of embodying low-density and compress askew small, and with relatively low cost, disclosure satisfy that other same performances use field Requirement.
To achieve the above object, the technical solution adopted by the present invention is：A kind of low-shrinkage butadiene styrene rubber foaming sole material The preparation technology of material, it is characterised in that：Described preparation technology comprises the following steps：
1）By the white carbon of the butadiene-styrene rubber of 100 parts by weight and 20-30 parts by weight, the zinc oxide of 5.0-10.0 parts by weight and Fully mixing is uniform in banbury for the stearic acid of 1.0-5.0 parts by weight；
2）Again by the foaming agent azodicarbonamide of 0.5-5.0 parts by weight, the crosslinking agent peroxidating two of 0.1-2.0 parts by weight Isopropylbenzene and 0.5-5.0 parts by weight sulphur, accelerator and 0.5-5.5 parts by weight paraffin are added in banbury, and kneading to mix Thing；
3）By step（2）The mixture of gained is pressed into the sheet material that thickness is 1-5 mm on open type dual-roller kneading machine；
4）Vulcanizer is embedded into mould in advance and is heated to 190-200 DEG C, the aqueous breast of upper polysiloxanes is then equably sprayed Liquid releasing agent, treats the complete use of water evaporation；
5）By step（3）The sheet material of gained is put into vulcanizer, cooled down at molding crosslinked foaming shaping slice, 20 DEG C, Obtain butadiene styrene rubber foaming material for sole of shoe.
Described step 1）The mixing temperature of middle banbury is 100-110 DEG C, and mixing time is that 5 min, rotating speed are 30- 50 rpm/min。
Described step 2）In accelerator be tetramethylthiuram disulfide, N- rings ethyl -2-[4-morpholinodithio time sulphonyl Amine and each 0.167 parts by weight of benzothiazole disulfide.
Described butadiene-styrene rubber uses styrenic monomer units content for 22%-25%.
Compared with prior art, the invention has the advantages that and effect：
The present invention is using compounding cross-linking system（Sulphur-cumyl peroxide）The SBR Foamed Sole Materials of preparation are compared Have that preferable combination property, i.e. shrinkage factor are low, density is small in traditional expanded material, hardness, resilience is moderate and compresses askew It is small, and cost is relatively low.Its shrinkage factor can be reduced to 2%, density for 0.21-0.35 g/cm3, compress it is askew be 15-25%, hardness （A）It is 55-60% for 40-60 °, resilience.
4th, embodiment
The present invention is described in further details with reference to specific embodiment：
Embodiment one：
（1）By the white carbon of 20 parts by weight and the styrene butadiene rubber sbr of 6 part by weight of zinc oxide and 100 parts by weight in banbury In fully mixing it is uniform, mixing temperature is 110 DEG C, and mixing time is that 5 min, rotating speed are 45 rpm/min；
（2）Again by the foaming agent azodicarbonamide of 4.0 parts by weight, the crosslinking agent cumyl peroxide of 0.6 parts by weight Sulphur, accelerator with 0.5 parts by weight（Tetramethylthiuram disulfide, N- rings ethyl -2-[4-morpholinodithio sulfenamide, two sulphur Change each 0.167 parts by weight of benzothiazole）And 5.0 the stearic acid of the parts by weight of paraffin 2.0 of parts by weight be added in banbury, knead Obtain mixture；
（3）By step（2）The mixture of gained is pressed into the sheet material that thickness is about 3 mm on open type dual-roller kneading machine；
（4）Vulcanizer is embedded into mould in advance and is heated to 200 DEG C, the aqueous emulsion of upper polysiloxanes is then equably sprayed Releasing agent, treats the complete use of water evaporation；
（5）By step（3）The sheet material of gained is put into vulcanizer, cooled down at pressing mold crosslinked foaming shaping slice, 20 DEG C, Obtain SBR foaming sole materials；
Wherein, SBR uses styrenic monomer units content for 22%-25%.
The expanded material shrinkage factor prepared by embodiment one is that 2.25%, density is 0.2236 g/cm3, compress and askew be 17.5%th, hardness（A）It is 59% for 54.2 °, resilience.
Embodiment two：
The SBR of the white carbon of 25 parts by weight and 9 part by weight of zinc oxide and 100 parts by weight is fully kneaded in banbury equal Even, mixing temperature is 110 DEG C, and mixing time is that 5 min, rotating speed are 35 rpm/min；
（2）Again by the foaming agent azodicarbonamide of 3.0 parts by weight, the crosslinking agent cumyl peroxide of 0.2 parts by weight Sulphur, accelerator with 0.5 parts by weight（Tetramethylthiuram disulfide, N- rings ethyl -2-[4-morpholinodithio sulfenamide, two sulphur Change each 0.167 parts by weight of benzothiazole）, the paraffin of 5 parts by weight and the stearic acid of 3.0 parts by weight be added in banbury, knead Obtain mixture；
（3）By step（2）The mixture of gained is pressed into the sheet material that thickness is about 3mm on open type dual-roller kneading machine；
（4）Vulcanizer is embedded into mould in advance and is heated to 200 DEG C, the aqueous emulsion of upper polysiloxanes is then equably sprayed Releasing agent, treats the complete use of water evaporation；
（5）By step（3）The sheet material of gained is put into vulcanizer, cooled down at pressing mold crosslinked foaming shaping slice, 20 DEG C, Obtain SBR foaming sole materials；
Wherein, SBR uses styrenic monomer units content for 22%-25%.
The expanded material shrinkage factor prepared by embodiment two is that 3.75%, density is 0.276 g/cm3, compress and askew be 24.5%th, hardness（A）It is 58% for 46.4 °, resilience.
Embodiment three：
The SBR of the white carbon of 25 parts by weight and 6 part by weight of zinc oxide and 100 parts by weight is fully kneaded in banbury equal Even, mixing temperature is 110 DEG C, and mixing time is that 5 min, rotating speed are 40 rpm/min；
（2）Again by the foaming agent azodicarbonamide of 3.0 parts by weight, the crosslinking agent cumyl peroxide of 0.4 parts by weight Sulphur, accelerator with 0.5 parts by weight（Tetramethylthiuram disulfide, N- rings ethyl -2-[4-morpholinodithio sulfenamide, two sulphur Change each 0.167 parts by weight of benzothiazole）, the paraffin of 5 parts by weight and the stearic acid of 1.0 parts by weight be added in banbury, knead Obtain mixture；
（3）By step（2）The mixture of gained is pressed into the sheet material that thickness is about 3 mm on open type dual-roller kneading machine；
（4）Vulcanizer is embedded into mould in advance and is heated to 200 DEG C, the aqueous emulsion of upper polysiloxanes is then equably sprayed Releasing agent, treats the complete use of water evaporation；
（5）By step（3）The sheet material of gained is put into vulcanizer, cooled down at pressing mold crosslinked foaming shaping slice, 20 DEG C, Obtain SBR foaming sole materials；
Wherein, SBR uses styrenic monomer units content for 22%-25%.
The expanded material shrinkage factor prepared by embodiment three is that 3.25%, density is 0.299 g/cm3, compress it is askew be 21%, Hardness（A）It is 61.2% for 52.4 °, resilience.
Example IV：
（1）The SBR of the white carbon of 20 parts by weight and 6 part by weight of zinc oxide and 100 parts by weight is fully mixed in banbury Refining is uniform, and mixing temperature is 110 DEG C, and mixing time is that 5 min, rotating speed are 30 rpm/min；
（2）Again by the foaming agent azodicarbonamide of 3.0 parts by weight, the crosslinking agent cumyl peroxide of 0.1 parts by weight The sulphur of 1.0 parts by weight, accelerator（Tetramethylthiuram disulfide, N- rings ethyl -2-[4-morpholinodithio sulfenamide, curing Each 0.167 parts by weight of benzothiazole）, the paraffin of 5 parts by weight and the stearic acid of 2.0 parts by weight be added in banbury, knead Mixture；
（3）By step（2）The mixture of gained is pressed into the sheet material that thickness is about 3 mm on open type dual-roller kneading machine；
（4）Vulcanizer is embedded into mould in advance and is heated to 200 DEG C, the aqueous emulsion of upper polysiloxanes is then equably sprayed Releasing agent, treats the complete use of water evaporation；
（5）By step（3）The sheet material of gained is put into vulcanizer, cooled down at pressing mold crosslinked foaming shaping slice, 20 DEG C, Obtain SBR foaming sole materials；
Wherein, SBR uses styrenic monomer units content for 22%-25%.
The expanded material shrinkage factor prepared by example IV is that 5.3%, density is 0.333 g/cm3, compress it is askew be 15.2%, Hardness（A）It is 54.6% for 55.2 °, resilience.

Claims (1)

1. a kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe, it is characterised in that：Described preparation technology bag Include following steps：
1）By the butadiene-styrene rubber of 100 parts by weight and the white carbon of 20-30 parts by weight, the zinc oxide and 1.0- of 5.0-10.0 parts by weight Fully mixing is uniform in banbury for the stearic acid of 5.0 parts by weight；
2）Again by the foaming agent azodicarbonamide of 0.5-5.0 parts by weight, the crosslinking agent peroxidating diisopropyl of 0.1-2.0 parts by weight Benzene and 0.5-5.0 parts by weight sulphur, accelerator and 0.5-5.5 parts by weight paraffin are added in banbury, knead to obtain mixture；
3）By step（2）The mixture of gained is pressed into the sheet material that thickness is 1-5 mm on open type dual-roller kneading machine；
4）Vulcanizer is embedded into mould in advance and is heated to 190-200 DEG C, the aqueous emulsion of upper polysiloxanes is then equably sprayed and takes off Mould agent, treats the complete use of water evaporation；
5）By step（3）The sheet material of gained is put into vulcanizer, cooled down at molding crosslinked foaming shaping slice, 20 DEG C, obtains Butadiene styrene rubber foaming material for sole of shoe；
Described step 1）The mixing temperature of middle banbury is 100-110 DEG C, and mixing time is that 5 min, rotating speed are 30-50 rpm；
Described step 2）In accelerator for tetramethylthiuram disulfide, N cyclohexyl 2 benzothiazole sulfenamide and Each 0.167 parts by weight of benzothiazole disulfide；
Described butadiene-styrene rubber uses styrenic monomer units content for 22%-25%.
CN201610229505.4A 2016-04-14 2016-04-14 A kind of preparation technology of low-shrinkage butadiene styrene rubber foaming material for sole of shoe Active CN105713262B (en)

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CN106432842B (en) * 2016-11-11 2018-10-30 陕西科技大学 Nano combined expanded material of high convergency stability butadiene-styrene rubber base and preparation method thereof
KR20230066128A (en) * 2018-05-31 2023-05-12 나이키 이노베이트 씨.브이. Cushioning member for article of footwear and related methods
CN109233024A (en) * 2018-07-13 2019-01-18 湖州市道场乡资产经营有限公司 A kind of light weight SBR foam sponge
CN108948466A (en) * 2018-07-13 2018-12-07 湖州市道场乡资产经营有限公司 A kind of low resilience high resiliency SBR foam sponge
CN110713641B (en) * 2019-10-25 2021-06-15 陕西科技大学 Preparation method of soft cushioning and tear-resistant sports insole material
CN111363210A (en) * 2020-03-18 2020-07-03 陕西科技大学 Ionic crosslinked rubber and preparation, recovery and secondary vulcanization method thereof
CN111704755A (en) * 2020-06-28 2020-09-25 陕西科技大学 Preparation method of rubber foam material with bubble inner wall shell
CN114835969A (en) * 2022-04-13 2022-08-02 茂泰(福建)鞋材有限公司 EVA sole, low-compression-deformation EVA foaming sheet and preparation method thereof

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EP1379578A4 (en) * 2001-02-23 2004-05-12 Phat Cushion Llc Foam cushion and method of making and using the same
TW200600310A (en) * 2004-06-21 2006-01-01 Microcell Composite Company High-rate foaming manufacturing method of thermoplastic elastomer composite

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